7.2.

2 Solution chemistry and temperature

In Fig. 7.1, the resistance of duplex alloys to see in sodium chloride solutions is presented 1. It
indicates that superduplex grades (e.g. S32750) are resistant to cracking in aerated 10 % Cl -
(i.e. 16.5% NaCl) with temperatures approaching 300C. These data sets have been compiled
using both practical experience and laboratory tests, although they do not tell the whole story.
For instance, the data are pertinent to aerated neutral solutions and so, if the oxygen content is
lowered, higher chloride concentrations can be tolerated, while more acidic conditions may
reduce resistance 1, 12 (Fig.7.6). On the other hand, limits for chloride concentration generated
with NaCl should be used with caution if Mg or Ca cations are present, due to their more
aggressive nature."

It has been demonstrate 13 in slow strain rate tests in laboratory conditions (e.g. deaerated 50
% LiCl2 at 100C) that low alloy duplex grades can be slightly more resistant than their more
highly alloyed cousins. This result can be obtained in such hot dilute acids with some chlorides,
where the low alloy grades suffer from general corrosion, such that any cracks that initiate are
immediately corroded and blunted. On the other hand, high alloy stainless steels are more
resistant to general corrosion, but could still crack due to the temperature, stress and presence
of chlorides. For this reason it is feasible that, under certain conditions, the more pitting
resistant grades can be more prone to cracking.

Care must be taken when using diagrams such as Fig.7.1to select material for a known (or
presumed) set of service conditions. For instance, in marine environments, the chloride
content is always in doubt due to evaporation, condensation and wetting. Further, evaporation
of seawater produces a concentration of Mg ions, which, in the extreme, can be equivalent to
boiling MgCl2 solution, with the added problem of a crevice formed by the salt deposit and a
supply of oxygen7. To simulate these conditions the continuous drop evaporation test using sea
water has been proposed 10, 14, 15. This test maybe too aggressive as wetting is not continuous in
practice, which allows for the steel to repassivate. Alternatively, an interrupted drip test has
been proposed 16 as more representative of service.

8 Welding metallurgy

8.1 Introduction

Welding metallurgy has played a key role in the alloy development of duplex stainless steels.
The earliest grades had high carbon contents and tended to form a ferrite-rich heat affected
zone (HAZ). Although some austenite reformation occurred due to these high carbon levels,
this also led to carbide precipitation and a loss in intergranular corrosion (IGC) resistance. Later
grades had lower carbon levels, but the high Cr/Ni ratio enhanced ferrite-rich micro-structures
in the HAZ and promoted grain growth.

In the early 1970s, a 22% Cr duplex stainless steel was developed. The patent' claimed that this
new steel was not sensitive to IGC upon welding due to a balanced chemistry including the
addition of nitrogen. However, the composition ranges permitted were very wide, which
allowed for melts to be produced which could still produce almost fully ferritic HAZs with an
associated reduction in corrosion resistance 2. Although the national specifications for the

22%Cr duplex stainless steel, (e.g.UNS S31803), still have quite wide ranges, most producers
and end users specify closer limits to control the weldability. In particular, nitrogen contents
within the upper range of the specification are common, as typified by the sub-set grade
S32205, and so the modern duplex stainless steels have a much better weldability than the
earlier grades (Fig.8.1).

8.2 HAZ transformations

The high temperature HAZ(HTHAZ) can be defined as the zone next to the fusion boundary
which approaches the melting point and will become almost completely ferritic on heating. On
the other hand, the low temperature HAZ (LTHAZ)is where the phase balance has remained
substantially unchanged. There are transitions between the LT and HT HAZ and the complexity
is increased further if repeated exposures from multipass welds are superimposed.

8.2.1 High temperature HAZ

The transformed microstructure in the HT HAZ is controlled only by the welding procedure and
steel composition 3, 4. With the arc energies normally used in practice, the problems associated
with almost fully ferritic zones (see Section 8.1) have largely been solved by means of
optimising the chemical composition of the base material. In particular, this has been done by
increasing the nitrogen levels of the steels, Fig. 8.1. As a result, the modern duplex steels
normally show ferrite levels in the HTHAZ in the range 50-70% , provided that appropriate
welding practices are used (Fig. 8.2).5

For a given steel composition, the microstructure in the HTHAZ is controlled by the imposed
thermal history and so heat input, material thickness, preheat and interpass temperatures are
all influential. More specifically, it is the peak temperature and exposure time to the single
phase ferritic region 3, 6 which controls austenite dissolution and ferrite grain size. Diffusion
controlled austenite reformation, which largely involves nitrogen redistribution, occurs at the
ferrite grain boundaries and by Widmansttten or intragranular side plate growth and can be
described 7 by CCT diagrams, as illustrated in Fig. 8.3. A large ferrite grain size has a retarding
effect on austenite formation.8

An experimental prediction model for the HTHAZ microstructure has been derived 9 for various
grades. Further, a theoretical kinetic model 10 for austenite reformation, assuming a nitrogen
controlled diffusion reaction has been developed. The latter model shows the beneficial effect
of a small ferrite grain size and gives a good correlation to experimental data. It also confirms
the faster austenite reformation in superduplex grades compared to 22 % Cr and low alloy
duplex grades.

Certain effects on HTHAZ may occur if welding is performed with fillers giving weld metals with
different nitrogen activities. During a weld thermal cycle the diffusion distance of nitrogen is
50-100 m. 11 Use of a nickel-base filler, such as type 625, will result in nitrogen migration into
the fused region and may increase the ferrite level in the HTHAZ. 12

In the HTHAZ, lower temperature reactions may occur in rapidly cooled welds, such as nitride
formation if insufficient austenite reformation takes place (see Section 3.4.6). However,
adjacent to the austenite phase a precipitate free zone is sometimes observed 13 in the ferrite,
as the nitrogen required for nitride precipitation has diffused to the austenite. Similarly, in
interpass regions, secondary austenite may precipitate (see Section 3.4.2).